Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
  • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J169/00—Adhesives based on polycarbonates; Adhesives based on derivatives of polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
  • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
  • C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
  • C09J123/24—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having ten or more carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J145/00—Adhesives based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Adhesives based on derivatives of such polymers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
  • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
  • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
  • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/20—Applications use in electrical or conductive gadgets
  • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
  • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
  • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
  • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
  • H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding

Definitions

• the present invention concerns a temporary bonding adhesive for temporarily bonding a semiconductor wafer during processing, and a method for manufacturing a semiconductor device using the same, and use of a resin composition as a temporary bonding adhesive.
• fragile wafers such as those in compound semiconductors may, in some cases, be damaged by mechanical grinding, so they are made thinner by etching.
• etching there are typically no problems if the amount of etching is such that the aim is merely stress removal, but in cases where several microns worth of ething is done, the BG tape may be deteriorated by the etching chemicals.
• a method has come to be utilized where bonding to a supporting substrate having a smooth surface is done, via a bonding material.
• a method using a supporting substrate is preferably utilized.
• Patent Documents 1 and 2 disclose polymers concerning the manufacture of a semiconductor device, although their aims differ from that of the present invention.
• a temporary bonding material was desired for which high precision processing is possible, it is easily detachable, and it does not readily remain on a semiconductor wafer. Additionally, a manufacturing method for a semiconductor device that decreases the damage to semiconductor wafers, makes high precision processing possible, and can shorten the time needed for thermal decomposition was desired.
• the aim of the present invention is to provide a temporary bonding adhesive for a semiconductor wafer that reduces damage to the semiconductor wafer, allows for high precision processing, and makes the detachment of the semiconductor wafer after treatment easy, and a method for manufacturing a semiconductor device that reduces damage to the semiconductor wafer, allows for high precision processing, and can shorten the time needed for thermal decomposition.
• a temporary bonding adhesive for a semiconductor wafer that temporarily fixes bonds a semiconductor wafer to a supporting substrate for processing the semiconductor wafer, and that is used after treatment for detaching the semiconductor wafer from the supporting substrate by heating.
• Said temporary bonding adhesive for a semiconductor wafer contains a resin composition such that the difference between the 95% weight loss temperature and the 5% weight loss temperature is 1 degree Celsius ⁇ (95% weight loss temperature) - (5% weight loss temperature) ⁇ 300 degrees Celsius.
• a temporary bonding adhesive for a semiconductor wafer that temporarily bonds a semiconductor wafer to a supporting substrate for processing the semiconductor wafer, and that is used after treatment for detaching the semiconductor wafer from the supporting substrate by heating, said temporary bonding adhesive for a semiconductor wafer containing a resin composition such that the difference between the 95% weight loss temperature and the 5% weight loss temperature is the following: 5 degree Celsius ⁇ (95% weight loss temperature) - (5% weight loss temperature) ⁇ 80 degrees Celsius.
• a method for manufacturing a semiconductor device comprising a step wherein a temporary bonding adhesive for a semiconductor containing a resin such that the difference between the 95% weight loss temperature and the 5% weight loss temperature is 5 degree Celsius ⁇ (95% weight loss temperature) - (5% weight loss temperature) ⁇ 80 degrees Celsius is provided on top of a supporting substrate in the form of a thin layer; a step wherein a semiconductor wafer is placed onto the surface of said supporting substrate provided with a layer, and the semiconductor wafer is stuck to said layer; a step wherein a semiconductor wafer is processed; and a step wherein said semiconductor wafer is removed from said supporting substrate by heating said layer.
• the temporary bonding adhesive for a semiconductor wafer of the present invention has the effects of reducing damage to the semiconductor wafer, making high precision processing possible, and making the detachment of the semiconductor wafer after treatment easy. Additionally, the method for manufacturing a semiconductor device using said temporary bonding adhesive for a semiconductor wafer has the effects of reducing damage to the semiconductor wafer, making high precision processing possible, and reducing the time needed for thermal decomposition.
• 5% weight loss temperature and “95% weight loss temperature” respectively refer to the temperature at which 5% and 95% of the weight is lost when measured by TG/DTA (thermogravimetry / differential thermal analysis).
• TG/DTA thermogravimetry / differential thermal analysis
• approximately 10 mg of the resin composition is precisely weighed, and measurement (atmosphere: nitrogen; rate of temperature rise: 5 degrees Celsius per minute) using a TG/DTA device (manufactured by Seiko Instruments) can be carried out.
• the temporary bonding adhesive for a semiconductor wafer according to the present embodiment is a temporary bonding adhesive for a semiconductor wafer that temporarily bonds a semiconductor wafer to a supporting substrate for processing the semiconductor wafer, and that is used after treatment for detaching the semiconductor wafer from the supporting substrate by heating, containing a resin composition such that the difference between the 95% weight loss temperature and the 5% weight loss temperature is 5 degree Celsius ⁇ (95% weight loss temperature) - (5% weight loss temperature) ⁇ 80 degrees Celsius.
• the temporary bonding adhesive for a semiconductor wafer having the above constitution contains a resin composition such that the difference between its 95% weight loss temperature and its 5% weight loss temperature is prescribed to be within the range 1 degree Celsius or more and 300 degrees Celsius or less, the temperature range needed for thermal decomposition of the temporary bonding adhesive will be narrow, so the time needed for thermal decomposition can be shortened, and damage to the semiconductor wafer can thereby be suppressed. Additionally, the effects of making the removal of the semiconductor wafer after treatment easy, and making it so that the temporary bonding adhesive does not readily remain on the semiconductor wafer are achieved. Additionally, since a wide temperature region over which it can be used stably can be secured, it is possible to make it available for various processing steps while still temporarily bonded to the supporting substrate. Additionally, since it can be formed as a layer on a supporting substrate having a smooth surface and with a sufficient precision, it achieves the effect of having a high precision for processing such as grinding.
• the aforementioned resin composition prefferably be such that the difference between the 95% weight loss temperature and the 5% weight loss temperature is 5 degree Celsius ⁇ (95% weight loss temperature) - (5% weight loss temperature) ⁇ 80 degrees Celsius.
• temperature region over which it can be used stably refers to the temperature region over which a semiconductor wafer can be held stably, without the temporary bonding adhesive breaking down. Since the temporary bonding adhesive according to the present embodiment can secure a wide region for this temperature region, it can be used for processing steps where heating is necessary, while the semiconductor wafer is still temporarily bonded to the supporting substrate. Whereby, the advantage can be had of being able to carry out differing steps successively.
• the aforementioned resin composition is preferably such that its 5% weight loss temperature is 50 degrees Celsius or greater.
• said resin composition is preferably such that its 50% weight loss temperature is 500 degrees Celsius or less. Whereby, as explained below, the effect can be obtained of preventing damage to the semiconductor device due to its heat history during the thermal decomposition step.
• the aforementioned resin composition such that the difference between its 95% weight loss temperature and its 5% weight loss temperature is prescribed to be within the range 1 degree Celsius or above and 300 degrees Celsius or below is not particularly restricted, but can be obtained by adjusting the molecular weight and the like of resins wherefor the bond strength of the main chain is low.
• the aforementioned resin composition such that the difference between its 95% weight loss temperature and its 5% weight loss temperature can be prescribed to be within the range 1 degree Celsius or above and 300 degrees Celsius or below is not particularly restricted, but it may be, for example, a norbornene based resin, a polycarbonate based resin, a polyester based resin, a polyamide based resin, a polyimide based resin, a polyether based resin, a polyurethane based resin, a (meta) acrylate based resin, or the like.
• the thermal decomposition of the temporary bonding adhesive during semiconductor device manufacturing processes such as a layer forming step, a bonding together step, a processing step, and the like, can be prevented, and further, the time for thermally decomposing the temporary bonding adhesive during the heating step can be shortened.
• these resin compositions norbornene based resins, or polycarbonate based resins are preferable, since they can effectively prevent thermal decomposition of the temporary bonding adhesive during semiconductor device manufacturing processes, and further, they can effectively shorten the thermal decomposition time for the temporary bonding adhesive during the heating step.
• the thermal decomposition time at the 50% weight loss temperature is 1 minute or longer, and 120 minutes or shorter.
• the thermal decomposition temperature higher than the minimum value given above, the rapid thermal decomposition of the temporary bonding adhesive can be suppressed, and since it will become possible to exhaust the thermally decomposed gas with an exhaust system, the contamination of the semiconductor device or the facility for manufacturing semiconductor devices can be prevented.
• the time required for the thermal decomposition step can be shortened, so that the productivity of semiconductor devices can be improved.
• the aforementioned thermal decomposition time may be measured by the following method.
• the 5% weight loss temperature is calculated using the method given above.
• approximately 10 mg of the aforementioned resin composition is precisely weighed, and next, the temperature is raised from 25 degrees Celsius to the 5% weight loss temperature in 30 minutes, and further, the measurement temperature is maintained at the 5% weight loss temperature, and measurement is carried out. From the obtained measured values, the time at which the 5% weight loss temperature is reached is defined as the starting point (0 minutes), and the time required to reach the 95% weight loss temperature is defined as the aforementioned decomposition time.
• the decomposition time at the 5% weight loss temperature is 1 minute or longer, and 60 minutes or shorter.
• the thermal decomposition temperature higher than the minimum value given above, the rapid thermal decomposition of the temporary bonding adhesive can be suppressed, and since it will become possible to exhaust the thermally decomposed gas with an exhaust device, so that contamination of the semiconductor device or the facility for manufacturing semiconductor devices can be prevented.
• the time required for the thermal decomposition step can be shortened, so that the productivity of semiconductor devices can be improved.
• the aforementioned norbornene based resins are not particularly restricted, but as examples, resins which include structural units as shown in the General Formula (1) given below, can be given.
• R 1 to R 4 are each one of hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, an aromatic group, an alicyclic group, a glycidyl ether group, or one of the substituent groups (2) given below. Additionally, m is an integer from 0 to 4.
• R 5 is either a hydrogen group, a methyl group, or an ethyl group
• R 6 , R 7 , and R 8 are either a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkoxy group having 1 to 20 carbon atoms, a linear or branched alkyl carbonyloxy group having 1 to 20 carbon atoms, a linear or branched alkyl peroxy group having 1 to 20 carbon atoms, or a substituted or non-substituted aryloxy group having 6 to 20 carbon atoms.
• n is an integer from 0 to 5.
• the aforementioned linear or branched alkyl group having 1 to 20 carbon atoms is not particularly restricted, but for example, it may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, or a decyl group or the like.
• a butyl groups or a decyl group having an excellent compatibility with each type of component comprising the temporary bonding adhesive, or solubility with each type of solvent, or further, mechanical properties when a semiconductor wafer and a supporting substrate are temporarily bonded, is preferable.
• the aforementioned aromatic group is not particularly restricted, but for example, it may be a phenyl group, a phenytyl group, a naphthyl group, or the like, but among these, a phenytyl group or a naphthyl group that has excellent mechanical properties when a semiconductor wafer and a supporting substrate are temporarily bonded, is preferable.
• the aforementioned alicyclic group is not particularly restricted, but for example, it may be a trimer or the like such as a cyclohexyl group, a norbornenyl group, a dihydro dicyclopenta diethyl group, a tetracyclo dodecyl group, a methyl tetracyclo dodecyl group, a tetracyclo dodeca diethyl group, a dimethyl tetracyclo dodecyl group, an ethyl tetracyclo dodecyl group, an ethylidenyl tetracyclo dodecyl group, a phenyl tetracyclo dodecyl group, or a cyclopenta diethyl group.
• a cyclohexyl group, or a norbornenyl group having excellent mechanical properties when a semiconductor wafer and a supporting substrate are temporarily bonded, and further, excellent
• R 5 in the aforementioned substituent group (2) is not particularly restricted as long as it is a hydrogen atom, or a methyl group, or an ethyl group, but a hydrogen atom, having excellent thermal decomposability during heat treatment, is preferable.
• R 6 , R 7 , and R 8 in the aforementioned substituent group (2) are not particularly restricted as long as they are each either a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkoxy group having 1 to 20 carbon atoms, a linear or branched alkyl carbonyloxy group having 1 to 20 carbon atoms, a linear or branched alkyl peroxy group having 1 to 20 carbon atoms, or a substituted or non-substituted aryloxy group having 6 to 20 carbon atoms.
• Such a substituent group may, for example, be a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, an acetoxy group, a propyoxy group, a gutyloxy group, a methylperoxy group, an isopropylperoxy group, a t-butylperoxy group, a phenoxy group, a hydroxyphenoxy group, a naphthyloxy group, a phenoxy group, a hydroxyphenoxy group, a naphthyloxy group or the like, and among these, a methoxy group, an ethoxy group, or a propoxy group, having excellent adhesiveness with the supporting substrate during temporary bonding, and excellent mechanical properties during semiconductor wafer processing, is preferable.
• m is an integer from 0 to 4, and it is not particularly restricted, but it is preferably 0 or 1. If m is 0 or 1, then the structural unit shown in said General Formula (1) can be represented by General Formula (3) or (4) given below.
• R 1 through R 4 are each either hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, an aromatic group, an alicyclic group, a glycidyl ether group, or one of the substituent groups (2).
• n is an integer from 0 to 5, and it is not particularly restricted, but it is preferable for n to be 0. If n is 0, the silyl group is directly bonded to the polycyclic ring via a silicon-carbon bond, so both heat decomposability of the temporary bonding adhesive and mechanical properties during semiconductor wafer processing can be achieved.
• the structural unit designated by the aforementioned General Formula (1) is not particularly restricted, but it can be obtained by polymerizing norbornene based monomers such as norbornene, 5-methyl norbornene, 5-ethyl norbornene, 5-propyl norbornene, 5-butyl norbornene, 5-pentyl norbornene, 5-hexyl norbornene, 5-heptyl norbornene, 5-octyl norbornene, 5-nonyl norbornene, 5-decyl norbornene, 5-phenetyl norbornene, 5-triethoxy silyl norbornene, 5-trimethyl silyl norbornene, 5-trimethoxy silyl norbornene, 5-methyl dimethoxy silyl norbornene, 5-dimethyl methoxy norbornene, or 5-glicydyl oxymethyl norbornene.
• norbornene based monomers such as norbornene, 5-methyl norbornene, 5-eth
• a single norbornene based monomer may be polymerized, or a plurality of norbornene based monomers may be copolymerized.
• norbornene based monomers 5-butyl norbornene, 5-decyl norbornene, 5-phenetyl norbornene, 5-triethoxy silyl norbornene, and 5-glicydyl oxymethyl norbornene, having excellent mechanical properties when a semiconductor wafer and a supporting substrate are temporarily bonded, are preferable.
• the aforementioned norbornene based resins are not particularly restricted, and they may be formed with a single structural unit shown in said General Formula (1), or formed with a plurality of structural units.
• norbornene based resins are homopolymers such as polynorbornene, polymethyl norbornene, polyethyl norbornene, polypropyl norbornene, polybutyl norbornene, polypentyl norbornene, polyhexyl norbornene, polyheptyl norbornene, polyoctyl norbornene, polynonyl norbornene, polydecyl norbornene, polyphenetyl norbornene, polytriethoxy silyl norbornene, polytrimethyl silyl norbornene, polytrimethoxy silyl norbornene, polymethyl dimethoxy silyl norbornene, polydimethyl methoxy silyl norbornene, or polyglycidyloxymethyl norbornene; or copolymers such as norbornene - triethoxysilyl norbornene copolymer, norbornene - glycidyl
• the weight average molecular weight of the aforementioned norbornene based resins is preferably from 10,000 to 1,000,000, and this is particularly preferably 30,000 to 800,000.
• the weight average molecular weight can be calculated as a polystyrene equivalent molecular weight by GPC (gel permeation chromatography) using THF as a solvent.
• the norbornene based resin having the structural unit designated by the aforementioned General Formula (1) is not particularly restricted, but may be synthesized by ring opening metathesis polymerization (herebelow also referred to as "ROMP"), a combination of ROMP and hydrogenation reaction, or radical polymerization or cationic polymerization.
• ROMP ring opening metathesis polymerization
• a combination of ROMP and hydrogenation reaction or radical polymerization or cationic polymerization.
• synthesis can be carried out using a catalyst containing a palladium ion source, a catalyst containing nickel and platinum, or a radical initiator, or the like.
• the aforementioned catalyst containing a palladium ion source is not particularly restricted, the compounds designated by the following General Formula (5) can be given.
• L is a ligand containing 1, 2, or 3 pi bonds
• X is a ligand containing 1 sigma bond and 0 to 3 pi bonds
• n is an integer from 0 to 2
• m is either 0 or 1.
• m and n are never simultaneously 0, and additionally, when m is 0, a is 2, and when m is 1, a is 1.
• CA is a weakly coordinating counterion.
• the "weakly coordinating counterion" in said General Formula (5) refers to an anion that is easily substituted by a neutral Lewis base due to being weakly coordinated with a cation.
• the ligand L in the aforementioned General Formula (5) is a ligand that is weakly coordinated to a palladium cation complex. Since this ligand L is relatively inactive, by reducing the ligand L, it can be easily removed from a cation complex by introducing a monomer into a growing polymer chain.
• the ligand L is not particularly restricted, but examples are mono-olefins having 2 to 12 carbon atoms (e.g., 2,3-dimethyl-2-butane), di-olefins having 4 to 12 carbon atoms (e.g., norbornadiene), or aromatic groups having 6 to 20 carbon atoms, and preferably the ligand L may be a chelated 2-position coordinating cyclic diolefin having 6 to 12 carbon atoms, for example, cyclo-octadiene (herebelow, also referred to as "COD”), dibenzo-COD, or an aromatic compound such as benzene, toluene, or mesitylene.
• COD cyclo-octadiene
• dibenzo-COD dibenzo-COD
• aromatic compound such as benzene, toluene, or mesitylene.
• the ligand X in the aforementioned General Formula (5) is not particularly restricted, but may be selected from (i) a group wherein a single carbon-metal sigma bond (not a pi bond) is imparted to a palladium in a cation complex, or (ii) a group wherein a single metal-carbon sigma bond and 1 to 3 pi bonds are imparted to a palladium in a cation complex.
• this group is bonded to the palladium with a single metal-carbon sigma bond and a non-pi bond, and it is not particularly restricted, but for example it may be a methyl group, an ethyl group, a linear or branched chain propyl group, a butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an aralkyl group with 7 to 15 carbon atoms, a benzyl group, or the like.
• the cation has a hydrocarbyl group that is directly bonded to the palladium by a single metal-carbon sigma bond, and similarly by at least 1 and not more than 3 pi bonds.
• the hydrocarbyl group by imparting a carbon-metal sigma bond and 1 to 3 olefinic pi bonds that may be conjugated or non-conjugated, the palladium metal cation complex can be stabilized.
• the hydrocarbyl group is not particularly restricted, but it may be a non-cyclic, monocyclic, polycyclic, linear or branched chain alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 15 carbon atoms, or an alkynyl group having 3 to 20 carbon atoms that may be substituted with a halo group (e.g., Cl and F).
• a halo group e.g., Cl and F
• the ligand X in the aforementioned General Formula (5) is a single aryl ligand that has a single sigma bond and a single pi bond, or a cationic form thereof, or alternatively, a compound that imparts at least one olefinic pi bond to a metal, and a single sigma bond to a metal from a distant carbon atom that is separated from both olefinic carbon atoms, by at least 2 carbon-carbon single bonds (iii).
• the palladium cation complex is weakly coordinated by the solvent with which the reaction is carried out.
• the aforementioned solvent is not particularly restricted, but halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2- dichloromethane, and aromatic hydrocarbons such as benzene, toluene, mesitylene, chlorobenzene, and nitrobenzene may be given as examples.
• Formula (6) shows a mode wherein said ligand X of (i) is a methyl group that is bonded to a palladium atom through a single metal-carbon sigma bond, and the ligand L is a COD that is weakly coordinated to a palladium metal through two olefinic pi bonds.
• R 9 , R 10 , and R 11 are each either a hydrogen, a linear or branched chain alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an alicyclic group having 5 to 6 carbon atoms.
• Formula (7) given above shows a mode wherein L does not exist, but an aromatic group that imparts three pi bonds is weakly coordinated to the palladium metal, and additionally, X is an aryl group that imparts a single metal-carbon sigma bond and an olefinic pi bond with the palladium.
• Formula (8) given above shows a mode wherein L is a COD, and X is an aryl group that imparts a single metal-carbon sigma bond and an olefinic pi bond with the palladium.
• Formula (9) given above shows a mode wherein X is an unsaturated hydrocarbon group that imparts an o-metal-carbon sigma bond, one conjugate pi bond, and two adduct pi bonds with the palladium.
• Formula (10) and (11) given below show modes wherein (iii) L is a COD, X is a ligand that imparts at least one olefinic pi bond to a palladium metal, and a single sigma bond to a metal from a distant carbon atom that is separated from, with space in between, both olefinic carbon atoms, by at least 2 carbon-carbon single bonds.
• the palladium cation complex described above associates with a relatively inactive, weakly coordinating or non-coordinating, counteranion CA weakly nucleophilic agent, and becomes a cation complex that is soluble in a solvent.
• the design of the anion species must be such that it is stable relative to reactions with the cationic palladium complex in the catalysis species, it is inactive, and it is soluble in the solvent.
• the aforementioned anion is not particularly restricted, but tetrafluorides of Ga, Al, B; hexafluorides of P, Sb, and As; perfluoro-acetate; propionate; butyrate; hydrated perchlorate; toluene sulfonate; trifluoromethylsulfonate; and substituted tetraphenylborate wherein the phenyl ring is substituted with fluoride or a trifluoromethyl group may be given as examples.
• the aforementioned counterion is not particularly restricted, but BF 4 - , PF 6 - , AlF 3 O 3 SCF 3 - , SbF 6 - , SbF 5 SO 3 F - , AsF 6 - , trifluoro acetate (CF 3 CO 2 - ), pentafluoro propionate (C 2 F 5 CO 2 - ), heptafluoro butyrate (CF 3 CF 2 CF 2 CO 2 - ), perchlorate (ClO 4 - •H 2 O), p- toluene- sulfonate (p-CH 3 C 6 H 4 SO 3 - ), and the compounds shown in the Formula (12) given below can be given as examples.
• R' is either hydrogen, fluoride, or tricluoromethyl, and n is 1 through 5.
• the compound shown in the following Formula (13) is preferable.
• the compound shown in the aforementioned Formula (13) comprises a weakly coordinating counteranion and a pi-aryl palladium complex, and is a compound having an arylic functionality, wherein the aryl group of the cation complex is bonded by a single carbon-palladium sigma bond and an olefinic pi bond.
• any two of R 9 , R 10 , and R 11 may be bonded together, and may form a cyclic, or a polycyclic structure.
• the polycyclic structure is not particularly restricted, but may, for example, be a carbon ring, or a heterocyclic ring. It is preferable for any two of R 9 , R 10 , and R 11 to bond together and form a ring having 5 to 20 atoms.
• the atoms forming heterocyclic rings are not particularly restricted, but they may, for example, be nitrogen, sulfur, or the like.
• R 14 is hydrogen, or a linear or branched chain alkyl group having 1 to 5 carbon atoms
• R 15 is a methylcarbonyl group
• R 16 is a linear or branched chain alkyl group having 1 to 20 carbon atoms.
• a multicomponent-based catalyst that contains one or both of a palladium ion source and an organic aluminum compound, and a third component, may be used.
• the aforementioned palladium ion source is not particularly restricted, and may be selected from compounds containing palladium, but the compounds containing palladium are preferably soluble in the reaction medium.
• the aforementioned compound containing palladium comprises an ionic and/or neutral ligand that is bonded to a palladium metal.
• the ionic and neutral ligand may be selected from various types of monodentate ligands, bidentate ligands, or molecular fragments of multidentate ligands, and combinations thereof.
• the ionic ligands that bond to palladium and generate compounds containing palladium are not particularly restricted, but they may be, for example, anionic ligands such as halides such as chloride, bromide, iodide, and fluoride ions; pseudohalides such as cyanide, cyanate, thiocyanate, hydrides and the like; branched and non-branched alkyl anions having 1 to 40 carbon atoms, carbanions such as phenyl anions and the like; cyclopentadienylide anions; pi aryl groups; halogenized acetyl acetates such as acetyl acetate, 2,4-pentanedionate, 1,1,1,5,5,5- hexafluoro- 2,4-pentanedionate, 1,1,1- trifluoro- 2,4- pentanedionate; acidic oxides of carbon such as carboxylates and halogenized carboxylates (for
• the aforementioned compound containing palladium may contain a complex anion such as PF 6 - , AlF 3 O 3 SCF 3 - , SbF 6 - , and the compound shown in Formula (15) below.
• R" and X are independently a halogen atom selected from among Cl, F, I, and Br, or a substituted or non-substituted hydrocarbyl group.
• the aforementioned hydrocarbyl group is not particularly restricted, but for example, it may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a heneicosyl group, a docosyl group, a tricosyl group, a tetracosyl group, a pentacosyl group, and isomers thereof that are alkyl groups
• X includes the groups shown below in Formula (16).
• substituted hydrocarbyl group refers to one where one or more hydrogen atoms are substituted with a halogen atom such as Cl, F, Br, and I (e.g., as in perfluorophenyl groups); a hydroxyl; an amino; an alkyl; a nitro; a mercapto, or the like.
• a halogen atom such as Cl, F, Br, and I
• the aforementioned compound containing palladium is not particularly restricted, but it may contain, for example, organic ammonium, organic arsonium, organic phosphonium, and a cation such as the pyridium compounds shown in Formula (17) below.
• A represents nitrogen, arsenic, and phosphorus
• R 17 is selected from among hydrogen, a branched or unbranched alkyl group having 1 to 20 carbon atoms, a branched or unbranched alkenyl group having 2 to 20 carbon atoms, and, for example, a cycloalkyl having 5 to 16 carbon atoms such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like.
• R 18 and R 19 are selected from hydrogen, a branched or unbranched alkyl group having 1 to 50 carbon atoms, a branched or unbranched alkenyl group having 2 to 50 carbon atoms, and a cycloalkyl group having 5 to 15 carbon atoms. Additionally, n is an integer from 1 to 5.
• R 17 in the aforementioned Formula (17) is an alkyl group wherefor the solubility in an organic solvent improves, having 15 to 72 carbon atoms, preferably 25 to 48 carbon atoms, and even more preferably 21 to 42 carbon atoms.
• R 18 in the aforementioned Formula (17) is preferable for R 18 in the aforementioned Formula (17) to be a branched or unbranched alkyl group having 1 to 50 carbon atoms, and more preferable for it to be an alkyl group having 10 to 40 carbon atoms.
• R 19 in the aforementioned Formula (17) is preferable for R 19 in the aforementioned Formula (17) to be a branched or unbranched alkyl group having 1 to 40 carbon atoms, and more preferable for it to be an alkyl group having 2 to 30 carbon atoms.
• organic ammonium cation is not particularly restricted, but it may be, for example, tridecyl ammonium, methyltricapryl ammonium, tris (tridecyl) ammonium, or trioctyl ammonium, or the like.
• organic arsonium or organic phosphonium cation is not particularly restricted, but it may be, for example, tridecyl arsonium and phosphonium, methyltricapryl arsonium and phosphonium, tris (tridecyl) arsonium and phosphonium, or trioctyl arsonium and phosphonium, or the like.
• pyridinium cation is not particularly restricted, but it may be, for example, eicosyl-4-(1-butyl pentyl) pyridinium, docosyl-4-(13-pentacosyl) pyridinium and eicosyl-4-(1-butyl pentyl) pyridinium, or the like.
• the neutral ligand that bonds with palladium is not particularly restricted, but it may be, for example, an olefin; an acetylene; carbon monoxide; a nitrogen compound such as an oxide of nitrogen, ammonium, alkyl isocyanide, alkyl isocyanate, or alkyl isothiocyanate; pyridine and pyridine derivatives (e.g., 1,10-phenanthroline, 2,2'-dipyridyl), 1,4-dialkyl-1,3-diazabutadiene, 1,4-diaryl+ diazabutadiene, or the compounds shown in Formula (18) given below.
• an olefin an acetylene
• carbon monoxide a nitrogen compound such as an oxide of nitrogen, ammonium, alkyl isocyanide, alkyl isocyanate, or alkyl isothiocyanate
• pyridine and pyridine derivatives e.g., 1,10-phenanthroline, 2,2'-dipy
• R 20 is a hydrocarbyl group or a substituted hydrocarbyl group, and n is an integer from 2 to 10.
• the compound shown in the aforementioned Formula (18) is not particularly restricted, but for example, it may be an amine; a urea; a nitrile such as acetonitrile, penzonitrile, and halogenized derivatives thereof; organic ethers such as cyclic ethers such as dimethyl ether of diethylene glycol, dioxane, tetrahydrofuran, furan diaryl ether, diethyl ether, diethylene glycol cyclic oligomers; organic sulfides such as thioethers; arsines; stibines; phosphines such as triaryl phosphine, trialkyl phosphine, bis (diphenyl phosphino) ethane, bis (diphenyl phosphino) propane, bis (dimethylp hosphino) propane, bis (diphenyl phosphino) butane, (S)- (-) 2,2'- bis (diphenyl
• R 20 represents a hydrocarbyl group or a substituted hydrocarbyl group; a phosphorus oxyhalide; a phosphonate; a phosphonite; a phosphinite; a ketone; or a sulfoxide such as an alkylsulfonide having 1 to 20 carbon atoms, an arylsulfoxide having 6 to 20 carbon atoms, or an alkaryl sulfonide having 7 to 40 carbon atoms.
• the abovementioned palladium source is not particularly restricted, but it may be, for example, palladium ethyl hexanoate, trans-PdCl2(PPh3)2, palladium (II) bis (trifluoroacetate), palladium (II) bis (acetylacetonate), palladium (II) 2-ethyl hexanoate, Pd (acetate)2 (PPh3)2, palladium (II) bromide, palladium (II) chloride, palladium (II) iodide, palladium (II) oxide, monoacetonitrile tris (triphenyl phosphine) palladium (II) tetrafluoro borate, tetrakis (acetonitrile) palladium (II) tetrafluoro borate, dichloro bis (acetonitrile) palladium (II), dichloro bis (triphenyl phosphin
• the aforementioned organic aluminum compound is not particularly restricted, but may be, for example, the compound shown in Formula (20) below.
• R 21 represents a branched or unbranched alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 24 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a cycloalkyl having 3 to 10 carbon atoms
• Q is a halide or a pseudohalide such as chlorine, fluorine, bromine, iodine, a branched or unbranched alkoxy having 1 to 20 carbon atoms, or an aryloxy
• x is 0 to 2.5.
• the aforementioned aluminum compound is not particularly restricted, but it may be, for example, a trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, triisobutyl aluminum, tri-2-methyl butyl aluminum, tri-3-methyl butyl aluminum, tri-2-methyl pentyl aluminum, tri-3-methyl pentyl aluminum, tri-4-methyl pentyl aluminum, tri-2-methyl hexyl aluminum, tri-3-methyl hexyl aluminum, trioctyl aluminum, or tris-2-norbornyl aluminum; or a dialkyl aluminum halide such as dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, or diisobutyl aluminum chloride; a monoalkyl aluminum dihalide such as methyl aluminum dichloride, ethyl aluminum dichloride, ethyl aluminum diiodide, propyl aluminum dichloride, isopropyl aluminum dichloride
• organic aluminum compounds, third component compounds, and compounds that comprise mixtures thereof may be used.
• the aforementioned third component compound is not particularly restricted, but it may be, for example, Lewis acids such as BF 3 -etherate, TiCl 4 , SbF 5 , tris (perfluorophenyl) boron, BCl 3 , or B(OCH 2 CH 3 ) 3 ; strong Bronsted acids such as hexafluoro antimonite (HSbF 6 ), HPF 6 hydrate, trifluoro acetate (CF 3 CO 2 H), FSO 3 H-SbF 6 , H 2 C(SO 2 CF 3 ) 2 CF 3 SO 3 H, or para toluene sulfonate; hexachloro acetone, hexafluoro acetone, 3-butenate-2,2,3,4,4-pentachloro butyl ester, hexafluoro glutarate, hexafluoro isopropanol, or chloranil; electron donating compounds such as phosphines and pho
• the method for using the aforementioned multi-component based catalyst is not particularly restricted, but a compound containing palladium, an organic aluminum compound, and a third component my be blended together in a hydrocarbon or a halo-hydrocarbon solvent, and next, this preliminary mixed catalyst system can be mixed into a reaction solvent comprising at least one norbornene based monomer, thereby polymerizing a norbornene based resin.
• the aforementioned reaction using a catalyst may be carried out in an organic solvent that does not act on the catalyst, and additionally, can dissolve the norbornene based monomer.
• the aforementioned organic solvent is not particularly restricted, but it may be, for example, an aliphatic hydrocarbon such as pentane, hexane, heptane, octane, or decane; an alicyclic hydrocarbon such as cyclopentane or cyclohexane; aromatic hydrocarbons such as benzene, chlorobenzene, nitrobenzene, toluene, and xylene; or a halogenized (polar) hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride, ethyl chloride, 1,1- dichloroethane, 1,2- dichloroethane, 1,2- dichloroethylene, 1- chloropropane, 2- chloropropane, 1- chlorobutane, 2- chlorobutane, 1-
• cyclohexanone or ethyl acetate may be similarly utilized.
• the selection of the reaction solvent is done based upon a large number of factors, including the selection of the catalyst, and whether it is desirable to carry out the polymerization with a slurry method or a solution method.
• Solvents that are preferable for a large proportion of the catalysts described for the present invention are chlorinated hydrocarbons such as methylene chloride or 1,2- dichloroethane, and aromatic hydrocarbons such as chlorobenzene and nitrobenzene.
• the mole ratio of the aforementioned norbornene based monomer to the catalyst containing palladium is preferably from 20:1 to 100,00:1, more preferably 200:1 to 20,000:1, and still more preferably 1,000:1 to 10,000:1.
• the mole ratio of the compound containing palladium to the organic aluminum compound is such that there is less of the aluminum compound than 100:1, and it is more preferable for it to be such that there is less of the aluminum compound than 30:1, and it is still more preferable for it to be such that there is less of the aluminum compound than 20:1.
• the mole ratio of the compound containing palladium to the third component may be within the range 0.25:1 to 20:1. If an acid is used for the aforementioned third component, it is preferable for there to be less of the acid than 4:1, and it is still more preferable for there to be less of the acid than 2:1.
• the polymerization temperature is preferably -100 to 120 degrees Celsius, and more preferably -60 to 90 degrees Celsius, and still more preferably -10 to 80 degrees Celsius.
• the aforementioned catalyst containing nickel and platinum is not particularly restricted, but the ones described in WO1997/033198 and WO2000/020472 may be used.
• the aforementioned catalyst containing nickel and platinum may be, for example, the compounds shown in the following Formula (21).
• the aforementioned catalyst containing nickel and platinum is not particularly restricted, but for example, it may be (toluene) bis (perfluorophenyl) nickel, (methylene) bis (perfluorophenyl) nickel, (benzene) bis (perfluorophenyl) nickel, bis (tetrahydro) bis (perfluorophenyl) nickel, bis (ethyl acetate) bis (perfluorophenyl) nickel, or bis (dioxane) bis (perfluorophenyl) nickel.
• toluene bis (perfluorophenyl) nickel
• methylene bis (perfluorophenyl) nickel
• benzene) bis (perfluorophenyl) nickel bis (tetrahydro) bis (perfluorophenyl) nickel, bis (ethyl acetate) bis (perfluorophenyl) nickel, or bis (dioxane) bis (perfluorophenyl) nickel.
• the mole ration of the aforementioned norbornene based monomer to the catalyst containing nickel and platinum is preferably from 20:1 to 100,00:1, more preferably 200:1 to 20,000:1, and still more preferably 1,000:1 to 10,000:1.
• the polymerization temperature is preferably 0 to 70 degrees Celsius, more preferably 10 to 50 degrees Celsius, and still more preferably 20 to 40 degrees Celsius.
• radical initiator is not particularly restricted, but one described in the Encyclopedia of Polymer Science, John Wiley and Sons, 13708 (1988 ) may be used.
• radical initiator examples include azobisisobutyronitrile (AIBN), benzoyl peroxide, lauryl peroxide, azobis iso-capronitrile, azobis isovaleronitrile, and t-butyl hydrogen peroxide, and the like.
• AIBN azobisisobutyronitrile
• benzoyl peroxide lauryl peroxide
• azobis iso-capronitrile azobis isovaleronitrile
• t-butyl hydrogen peroxide examples of the aforementioned radical initiator.
• the polymerization temperature thereof is preferably 50 to 150 degrees Celsius, more preferably 60 to 140 degrees Celsius, and still more preferably 70 to 130 degrees Celsius.
• the aforementioned polycarbonate based resin is not particularly restricted, but it may be, for example, polypropylene carbonate, polyethylene carbonate, 1,2- polybutylene carbonate, 1,3- polybutylene carbonate, 1,4-polybutylene carbonate, cis- 2,3- polybutylene carbonate, trans- 2,3 -polybutylene carbonate, ⁇ , ⁇ - polyisobutylene carbonate, ⁇ , ⁇ - polyisobutylene carbonate, cis- 1,2- polycyclobutylene carbonate, trans- 1,2- polycyclobutylene carbonate, cis- 1,3- polycyclobutylene carbonate, trans- 1,3- polycyclobutylene carbonate, polyhexene carbonate, polycyclopropene carbonate, polycyclohexene carbonate, poly (methylcyclohexene carbonate), poly (vinyl cyclohexene carbonate), polydihydro naphthalene carbonate, polyhexahydro
• polycarbonate based resins are polypropylene carbonate / polycyclohexene carbonate copolymer, poly [(oxy carbonyl oxy- 1,1,4,4- tetramethyl butane)- alt- (oxycarbonyl oxy- 5-norbornene- 2- endo- 3- endo- dimethane)], poly [(oxy carbonyl oxy- 1,4-dimethyl butane)- alt- (oxy carbonyl oxy- 5- norbornene- 2- endo- 3- endodimethane)], poly [(oxy carbonyl oxy- 1,1,4,4- tetramethyl butane)- alt- (oxy carbonyl oxy- p- xylene)], and poly [(oxy carbonyl oxy- 1,4- dimethyl butane)-alto- (oxy carbonyl oxy- p- xylene)].
• the weight average molecular weight (Mw) of the aforementioned polycarbonate is 1,000 to 1,000,00, and more preferable for it to be 5,000 to 800,000.
• Mw weight average molecular weight
• the wettability of the temporary bonding adhesive to the semiconductor wafer or supporting body during the layer forming step can be improved, and further, the effect of improved film formability can be obtained.
• the compatibility with each of the components comprising the temporary bonding adhesive, and the solubility in various types of solvents and further, the effect of improved thermal decomposability of the temporary bonding adhesive during the heating step can be obtained.
• the method for polymerizing the aforementioned polycarbonate based resin is not particularly restricted, but publicly known polymerization methods such as, for example, the phosgene method (solvent method) or the ester exchange method (melting method), may be used.
• the aforementioned resin compositions are preferably blended in so that their proportion is 10% to 100% of the entire amount of the temporary bonding adhesive. More preferably, they should be blended in so that their proportion is 30% to 100%. This is because, by making the contained amount of the resin composition higher than the aforementioned lower limit, the existence of residual temporary bonding adhesive on the semiconductor wafer or the supporting body after the detachment step described below, can be prevented.
• resin compositions particularly preferable are polypropylene carbonate, 1,4-polybutylene carbonate, butyl norbornenetriethoxysilyl norbornene copolymer, decylnorbornene- butylnorbornenephenetyl norbornene- glycidyl oxymethyl norbornene copolymer, and decyl norbornene- glycidyl oxymethyl norbornene copolymer.
• the aforementioned temporary bonding adhesive may contain a solvent.
• the solvent is not particularly restricted, but it may be a hydrocarbon such as mesitylene, decalin, and mineral spirits; an alcohol or an ether such as anisole, propylene glycol monomethyl ether, dipropylene glycol methyl ether, diethylene glycol monoethyl ether, and diglyme; an ester or a lactone such as ethylene carbonate, ethyl acetate, N-butyl acetate, ethyl lactate, 3-ethoxypropionate ethyl, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene carbonate, and ⁇ -butyrolactone; a ketone such as cyclopentanone, cyclohexanone, methyl isobutyl ketone, and 2-heptanone; or an amide or a lactam such as N- methyl-2- pyrori
• the contained amount of the aforementioned solvent is not particularly restricted, but it is preferably 5 to 98 wt%, and more preferably 10 to 95 wt%.
• the aforementioned temporary bonding adhesive may contain a photo initiator.
• the photo initiator is not particularly restricted, but it may be, for example, a photo radical initiator or a photo acid generating agent. If the resin composition contains a photo initiator, a resin composition can be formed at a desired position, by having an exposing and developing step.
• the aforementioned photo radical initiator is not particularly restricted, as long as it is a compound that it breaks down into two types of compounds or more by being irradiated with actinic rays, and at least one of the aforementioned compounds is a compound having free radicals, for example, bis (2,4,6- trimethyl benzoyl)- phenyl phosphin oxide (Irgacure 819, Ciba Specialty Chemicals Inc.), 2- benzyl- 2- dimethyl amino- 1- (4-morpholinophenyl)- butanone-1 (Irgacure 369, Ciba), 2,2- dimethoxy- 1,2-diphenyl ethane- 1- one (Irgacure 651, Ciba), 2-methyl- 1 [4- (methylthio)-phenyl]- 2- morpholinopropane- 1- one (Irgacure 907, Ciba), benzoin ethyl ether (BEE, Aldrich), 2- methyl- 4'-
• the aforementioned photo acid generating agent is not particularly restricted, as long as it is a compound that generates acid when irradiated with actinic rays, for example, nuclophilic halides, complex metal halide anions, or the like. More concrete examples are tetrakis (pentafluorophenyl) borate- 4-methylphenyl [4- (1-methyl ethyl) phenyl] iodonium (DPI-TPFPB), tris (4- t-butyl phenyl) sulfonium tetrakis- (pentafluoro phenyl) borate (TTBPS-TPFPB), tris (4- t- butyl phenyl) sulfonium hexafluoro phosphate (TTBPS-HFP), triphenyl sulfonium trifurate (TPS-Tf), bis (4- tert- butyl phenyl) iodonium trifur
• the contained amount of the aforementioned photo initiator, relative to 100 weight portions of the aforementioned resin composition, is preferably 0.1 to 10 weight portions, and more preferably 0.5 to 5 weight portions.
• the aforementioned temporary bonding adhesive may contain, along with the photo initiator, a sensitizer that is a component having the function of producing, or increasing, the reactivity of the photo initiator to a particular type or wavelength of light.
• the aforementioned sensitizer is not particularly restricted, but examples such as anthracene, phenanthrene, chrysene, benzpyrene, fluoranthene, rubrene, pyrene, xanthone, indanthrene, thioxanthene-9-one, 2-isopropyl- 9H- thioxanthene- 9- one, 4-isopropyl- 9H-thioxanthene- 9-one, 1-chloro- 4-propoxy thioxanthone, and mixtures thereof can be given.
• the contained amount of such sensitizers, relative to 100 weight portions of the sensitizer mentioned above, is preferably 100 weight portions or less, and more preferably 20 weight portions or less.
• the temporary bonding adhesive of the present invention may contain, in addition to the abovementioned components, for example, an acid scavenger.
• the aforementioned acid scavenger is a component that has the function of preventing acid that has been generated by the irradiation of light from dispersing to portions that have not been irradiated by light. That is, it is a component that has the function of preventing the unwanted curing of portions that have not been irradiated with light. By containing such an acid scavenger, the patterning precision can be made higher.
• amines secondary amines, tertiary amines
• tri (n-propy) amine triethylamine
• the compounds represented by the Formula (22) given below and the compounds represented by the Formula (23) below or the like, and mixtures thereof, can be given.
• R 22 is H or an alkyl group.
• R 23 through R 27 are H, or an arbitrary pair of them are methyl groups and the remainder are H.
• the contained amount of the aforementioned acid scavenger, relative to 100 weight portions of the photo initiator mentioned above, is preferably 0.01 to 2 weight portions, and more preferably 0.02 to 1 weight portion. Whereby, the unwanted curing of portions that have not been irradiated with light can be more effectively prevented.
• the aforementioned temporary bonding adhesive may contain an antioxidant.
• the aforementioned antioxidant has the function of preventing the generation of undesirable acids, and the native oxidation of the resin composition.
• the aforementioned antioxidant is not particularly restricted, but for example, Ciba IRGANOX (trademark) 1076, or Ciba IRGAFOS (trademark) 168, obtainable from Ciba Fine Chemicals Co. in Tarrytown, New York, can be used suitably.
• antioxidants such as Ciba Irganox (trademark) 129, Ciba Irganox 1330, Ciba Irganox 1010, Ciba Cyanox (trademark) 1790, Ciba Irganox 3114, and Ciba Irganox 3125, or the like, may be used.
• the contained amount of the aforementioned antioxidant, relative to 100 weight portions of the aforementioned resin composition is preferably 0.1 to 10 weight portions, and is more preferably 0.5 to 5 weight portions.
• the aforementioned temporary bonding adhesive may contain, as needed, an additive agent such as an acryl based, silicone based, fluorine based, or vinyl based leveling agent, silane coupling agent, or diluent.
• an additive agent such as an acryl based, silicone based, fluorine based, or vinyl based leveling agent, silane coupling agent, or diluent.
• the aforementioned silane coupling agent is not particularly restricted, but it may, for example, be 3-glycidoxy propyl trimethoxy silane, 3-glycidoxy propyl methyl diethoxy silane, 3-glycidoxy propyl triethoxy silane, p-styryl trimethoxy silane, 3-methacryloxy propyl methyl dimethoxy silane, 3-methacryloxy propyl methyl trimethoxy silane, 3-methacryloxy propyl methyl diethoxy silane, 3-methacryloxy propyl triethoxy silane, 3-acryloxy propyl trimethoxy silane, N-2- (amino ethyl)- 3-amino propyl methyl dimethoxy silane, N-2- (amino ethyl)- 3-amino propyl trimethoxy silane, N-2- (amino ethyl)-3-amino propyl triethoxy silane, 3-amino propyl trim
• the aforementioned diluent is not particularly restricted, but it may be, for example, a cycloether compound such as cyclohexane oxide or a-pinene oxide; an aromatic cycloether such as [methylene bis (4,1- phenylene oxymethylene)] bis oxirane; or a cycloaliphatic vinyl ether compound such as 1,4-cyclohexane dimethanol divinyl ether.
• a cycloether compound such as cyclohexane oxide or a-pinene oxide
• an aromatic cycloether such as [methylene bis (4,1- phenylene oxymethylene)] bis oxirane
• a cycloaliphatic vinyl ether compound such as 1,4-cyclohexane dimethanol divinyl ether.
• the method for manufacturing a semiconductor device comprises a step wherein a temporary bonding adhesive for a semiconductor wafer containing a resin composition wherefor the difference between the 95% weight loss temperature and the 5% weight loss temperature is 1 degree Celsius ⁇ (95% weight loss temperature) - (5% weight loss temperature) ⁇ 300 degrees Celsius is provided in the form of a thin layer on top of a supporting substrate; a step wherein a semiconductor wafer is placed upon the surface of the aforementioned supporting substrate whereon the layer was provided; a step wherein said semiconductor wafer is stuck together with the aforementioned layer; a step wherein the aforementioned semiconductor wafer is processed; and a step wherein the aforementioned semiconductor wafer is detached from the aforementioned supporting substrate by heating the aforementioned layer.
• the difference between the 95% weight loss temperature and the 5% weight loss temperature is prescribed to be in the range 1 degree Celsius or greater, and 300 degrees Celsius or less, so the temperature range needed for thermal decomposition of the temporary bonding adhesive is narrow, and the time needed for thermal decomposition can be shortened, thereby suppressing damage to the semiconductor wafer. Additionally, it achieves the effects of it being difficult for the temporary bonding adhesive to remain on the semiconductor wafer, and the detachment of the semiconductor wafer after processing becomes easy. Additionally, since a wide range over which it is stably usable can be secured, it becomes possible to submit it to various processing steps while temporarily bonded to the supporting substrate. Additionally, since it can be formed as a layer on top of a supporting substrate having a smooth and sufficiently precise surface, it achieves the effect of having a high precision during processing such as grinding.
• the aforementioned manufacturing method for a semiconductor device it is more preferable to contain a resin composition such that the difference between the 95% weight loss temperature and 5% weight loss temperature is 5 deg C ⁇ (95% weight loss temperature) - (5% weight loss temperature) ⁇ 80 deg C.
• the time required for thermal decomposition can be shortened, and the effect of being able to secure a wide temperature range over which it is stably usable can be even more improved.
• the abovementioned temporary bonding adhesive is utilized as a temporary bonding adhesive for a semiconductor wafer. That is, the temporary bonding adhesive used in the manufacturing method for a semiconductor device according to the present embodiment has the features of the abovementioned temporary bonding adhesive.
• the step where a thin layer of a temporary bonding adhesive is provided on a supporting substrate or a semiconductor wafer, in order to fix a semiconductor wafer on a given supporting substrate is carried out.
• the thin layer of a temporary bonding adhesive may be provided on either one of the supporting substrate or the semiconductor wafer.
• a method for providing the temporary bonding adhesive in the form of a thin layer it can be carried out using a publicly known method such as the spin coat method, spray method, printing method, film transcription method, slit coat method, scan coating method, and the like, so there is the advantage that no new investments in facilities are needed.
• the spin coat method is preferable, and it is preferable because it can form a uniform and flat thin layer.
• the step in which the aforementioned supporting substrate or semiconductor wafer is placed upon the surface of the supporting substrate or the semiconductor wafer whereon a thin layer is provided, and the aforementioned supporting substrate or semiconductor wafer is stuck together with the aforementioned thin layer is carried out.
• a device such as a vacuum press or a wafer bonder or the like may be used.
• the step wherein the semiconductor wafer that has been bonded on top of the supporting substrate with the temporary bonding adhesive is processed is carried out.
• the processing of the semiconductor wafer is grinding of the rear surface of the semiconductor wafer, etching for stress release, forming of Via holes, lithography, coating, vapor deposition, and the like.
• the method for manufacturing a semiconductor device according to the present embodiment since it can be formed as a thin layer on top of a supporting substrate having a smooth and sufficiently precise surface, so the effect of high precision in processing can be achieved.
• the temporary bonding adhesive in a form of a thin layer is heated and removed is carried out.
• its thermal decomposition temperature is such that the difference between its 95% weight loss temperature and its 5% weight loss temperature is restricted to the range of 1 degree Celsius or greater, or 300 degrees Celsius or less, so that the temperature range required for thermal decomposition of the temporary bonding adhesive is narrow, and the time required for thermal decomposition can be shortened. In this way, heat damage to the semiconductor wafer can be suppressed.
• detaching refers to the operation wherein the semiconductor wafer is peeled away from the supporting substrate.
• this operation may be carried out by the method of detaching in the vertical direction relative to the surface of the supporting substrate, the method of detaching by sliding in the horizontal direction relative to the surface of the supporting substrate, or the method of detaching by tilting up the semiconductor wafer from one side of the semiconductor wafer.
• residual temporary bonding adhesive that has remained on the semiconductor wafer or the supporting substrate may be removed.
• the removal method for the residual temporary bonding adhesive is not particularly restricted, but it may, for example, be plasma treatment, chemical immersion treatment, grinding treatment, or heat treatment.
• a temporary bonding adhesive was produced using the following compounds.
• 1,4-butanediol 168 g, 1.864 mol
• diethyl carbonate 264.2 g, 2.236 mol
• 1,4-butanediol 168 g, 1.864 mol
• diethyl carbonate 264.2 g, 2.236 mol
• 1,4-butanediol 168 g, 1.864 mol
• diethyl carbonate 264.2 g, 2.236 mol
• ethyl acetate 600 g
• cyclohexane 600 g
• 5-decyl norbornene 75.74 g : 0.323 moles
• 5-butyl norbornene 72.83 g : 0.485 moles
• 5-phenetyl norbornene 64.07 g : 0.323 moles
• 5-glycidyl oxymethyl norbornene 87.36 g : 0.485 moles
• the agitation was stopped, and after the separated water layer was removed, the remaining organic layer was added to 450 g of pure water and 150 g of isopropyl alcohol in three batches, and washing was done by agitation and removal. After washing, the organic layer was diluted with 400 ml of cyclohexane, and added to 6 times its amount of methanol (7200 ml), and the precipitated polymer was recovered by filtering. After air drying the obtained solid matter for 18 hours, and drying for 24 hours under a reduced pressure of 1 mmHg, 284.7 g (yield 95.8%) of the target substance was obtained in the form of a solid resin.
• the abovementioned system was raised from 40 degrees Celsius to 60 degrees Celsius over a period of 10 minutes, then the system was agitated for 3 hours while maintaining this temperature.
• a solution consisting of 34.0 g of glacial acetic acid and 64.1 g of 30% hydrogen peroxide solution added to approximately 98.0 g of pure water was added, and after agitating for 5 hours at 50 degrees Celsius, 20 g of isopropyl alcohol was added to the system. The agitation was stopped, and after the separated water layer was removed, the remaining organic layer was added to 60 g of pure water and 20 g of isopropyl alcohol in three batches, and washing was done by agitation and removal.
• the organic layer was diluted with 60 ml of cyclohexane, and added to 6 times its amount of methanol (960 ml), and the precipitated polymer was recovered by filtering. After air drying the obtained solid matter for 18 hours, and drying for 24 hours under a reduced pressure of 1 mmHg, 37.5 g (yield 93.8%) of the target substance was obtained in the form of a solid resin.
• the weight average molecular weight of the synthesized poly was measured by GPC, it was found to be 110,000.
• the 5% weight loss temperature, the 50% weight loss temperature, and the 95% weight loss temperature of the 1,4-polybutylene carbonate and the 5-decyl norbornene / 5-butyl norbornene / 5-phenetyl norbornene / 5-glycidyl oxymethyl norbornene 20 mol% / 30 mol% / 20 mol% / 30 mol% copolymer obtained in the abovementioned Embodiment 1 to 3 was measured (atmosphere : nitrogen, temperature rising rate : 5 degrees Celsius per minute) with a TG/DTA device (manufactured by Seiko Instruments). The results are shown in Table 1.
• Emb.1 Emb. 2 1,4-polybutylene carbonate Mw 35,000 100 g 5-decylnorbornene/5-butylnorbornene/5-phenetylnorbornene/ 5-glycidyloxymethylnorbornene (20 mol% / 30 mol% / 20 mol% / 30 mol%) 100 g anisole 900 g 2-heptanone 233.3 g 5% weight loss temperature (deg C) 277 274 50% weight loss temperature (deg C) 311 418 95% weight loss temperature (deg C) 330 533 Decomposition Time at 5% weight loss temperature (min) 10.0 Decomposition Time at 50% weight loss temperature (min) 105 (95% weight loss temp.) - (5% weight loss temp.) (deg C) 53 259
• the production of a semiconductor device was carried out.
• the temporary bonding adhesive obtained in the Embodiments was applied to an 8 inch transparent glass (rotation rate : 1,200 rpm, time : 30 seconds), and next, pre-baking was done on a hot plate at 120 degrees Celsius for 5 minutes, and a thin layer comprising the temporary bonding adhesive having a thickness of 5 ⁇ m was formed.
• a wafer bonder (Model Number SB-8e, manufactured by SUSS MicroTec) was used to temporarily fix an 8 inch silicon wafer (thickness 725 ⁇ m) to the 8 inch transparent glass through a thin layer comprising the temporary bonding adhesive (atmosphere : 10 -2 mbar, temperature : 160 degrees Celsius, load : 10 kN, time : 1 minute).
• the temporary bonding adhesive of Embodiment 1 was thermally decomposed at 320 degrees Celsius for 30 minutes. Additionally, the temporary bonding adhesive of Embodiment 2 was thermally decomposed at 450 degrees Celsius for 120 minutes.

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• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
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• Manufacturing & Machinery (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• General Physics & Mathematics (AREA)
• Physics & Mathematics (AREA)
• Computer Hardware Design (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Power Engineering (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Mechanical Treatment Of Semiconductor (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 2009
  • 2009-06-30 TW TW098121978A patent/TW201043658A/zh unknown
  • 2009-06-30 KR KR1020090059143A patent/KR20100134492A/ko unknown
  • 2009-11-06 EP EP09175317A patent/EP2264113A3/fr not_active Withdrawn
• 2010
  • 2010-06-15 KR KR1020117011403A patent/KR20120027102A/ko not_active Application Discontinuation
  • 2010-06-15 CN CN2010800033147A patent/CN102232104A/zh active Pending
  • 2010-06-15 JP JP2011519783A patent/JPWO2010147103A1/ja not_active Withdrawn
  • 2010-06-15 WO PCT/JP2010/060081 patent/WO2010147103A1/fr active Application Filing
  • 2010-06-15 US US13/126,934 patent/US20110263095A1/en not_active Abandoned
  • 2010-06-15 TW TW099119423A patent/TW201109414A/zh unknown
  • 2010-06-15 EP EP10789478A patent/EP2351805A4/fr not_active Withdrawn

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